Method of sealing off water and gas layers



r m A 15.10:

mnon or' snu'uggwammoas mm. and am new Development company. calm.

Application November-15, 1m; serial No. 174.651.

and oil welife'end n emioalinethodtior a Water and gas oiten 1cm parallel.

and closely wacent the oil traversed by a well. In; cases when it is difllcullf orimpossible to v cement of! these undesirable layers without at the sametinieinterierin: with theilowoto'ihchemm. lnvbhtion pertainito'thetreatmentoi m to a known as metal alcoholates. They are. stable,

to ical methods are used to preventwa'ter or iceesive amountcotias iromentcrlnsthe .well. Forthieiulri w atreatinc oschtisintroducedintotheweil-.'i'orcedintothelayertobe.

sealed oil. end caused to depositfpi'ecipitate in It the pores oi said layer, thereby substnntially'decreasins-its permeability to the dew or water or The proceeses which have so iarbeen used tor the chemical shut-oi! of oil wells are. however, not

no entirely satisfactory. Home or theee-proceses require the use of aeombina'tion oi aeveral.treat-, i s sc nt to form the p ume precipitate b1 chemicol reaction between said agents. which g g-Other methods are uncertain in their sineetheyrelyior thesame purpoeeonthe'pree ence in the .iormation-wmrs or some salts. Btill other-methodaule aaentsjwhich are 'unstable,-volatile, in their-elects. end

% so tend toiorin tothe eq lnmen v t.- I i iatfietoretheribiedtoitiiebreoentibvem flfl "(ll Aliplilticprimary, secondary, and tertiary .tion to provide a method ior'oeleetiveiy lealins oiiporoosiormationnniehuwaterandasiayas ers without interlerine with the homo! oil. by introducing lntdthewells and 'i'orcfill into the formation. certain metallic derivative! of. the al-. cohols capable r rennin; by hydrolysis wa msolublemctallic hydroxides which are depo'ai win the pores oi. the strata to be treatedand serv :glugorsealthe pofestothe-iiowoiwater as. The method of the present invention does. not require the use of several reagents, but maybe 45 carriedout. if desired. by meahs of a sinele treatin; solution.- the reaction occurring upon contact with connate water: oi any chemical composition. orwlth an aqueous charle iniected into the (emotion. The deposited motelso he hydroxides. being soluble gueid, can furthermore be easily removed acid treatment. tor example. in case the deposit hzdbeeninoor rectlyplaced .inan'hflbem er; r l to Themetallic derivatives ot the misused subscripts satlsf ii'roln th'e iormation by aocordinz to the present invention are those substantially neutral and non-volatile compounds which can be represented by the iormula:

whereinz-hl represents any metal which forms watcrofilllble or substantially water-insoluble. (for example, to the extent of 1 part in 10,000 parts or water), but preferably acid soluble hydm'xides, such as aiuminurpucopper, iron, tin, magnesium, zinc. le ."ehromiurnf mangan' e, nickel; and cobalt. e metals, for exam e, calcium. or barium, .whose hydroxides have a. somewhat greater solubility inpure water than that indicated above, may equally well be used, since the presence of various salts in the formation waters considerably decreases the solubility oi saidhydroxides, and makes them suitable tor the purposes of the present invention. C and 0 represent a carbon and an oxygen atom,'respectively. R1. Resend R: represent hydrogen atom. or alkyl or sryl radicals which may be substituted or not. The substituting groups may be selected from the groupconsistin: oi'ehalogens, 0.0K. NE, 80;, BCiL-mdBOa. :eandyarc yin: valence requirements.

In preparind the above metal alcoholetes the tollowin alcohols maybeusedasatartingmatesaturated and-unsaturated monohydric alsohol's, such as methyl, ethyl, isopropyl. tertiary butyl, secondary amyl. normal deeyl .alcohohproparzyl alcohol. etc. i

(a) Aliphatic polyhydrlc alcohols such a thyle ene glycol, trimethylene glycol. pro lene glycol, emylene elycols, hexylene c ycei'in, etc. i

(8) Arylalcohols, such asphenol, cresol, xylenol,

benzyl alcohol. phenyl-ethyl alcohol, phenyl-methyl cerbinol, etc.

(4) Substituted slcoholso! the above types, such as monoethanolamine, hydroxyamylsmine,

glycol ehlorhydrin; phenolic alcohols, etc. (iii Mixtures or any alcohols of the above types. Metallic slcoholates may he prepared from the above alcohols in a manner well known to the art. lbrexample, aluminum alcoholates of aloohols. snobs-e ethyl alcohol, etc. may be termed by direct reaction between activated aluminum and theaicohol. Alcoholates oi hlshcr boilinz alcohols, such as ethylene glycol, glycerol, monoethanolamine, etc., may be formed by metathetic reaction with the aluminum alcoholates of the lower alcohols.

In treating awell with any of the above alcoholates which are usually solid at ordinary temperatures, it is desirable to employ a solvent or a dispersing agent, which facilitates the handling of the treating agents and secures a gradual action subject tocontrol. The solvent or dispersing agents which are useful for this purpose may include any non-aqueous. material such as mineral oils, gasoline, naphtha, benzene, alcohols, esters, ketones carbon tetrachloride, carbon disulphide, etc. The concentration of the metal alcoholate in such liquids may be varied over wide limits, especially good results being obtained within the range from 10 to 50 per cent or-more by weight.

In applying the treatment of the present invention to an oil well in order to seal oil waterbearing formations, the following procedure may be followed: a

The well is first preferably filled with oil, and a desired amount of a non-aqueous solution consisting of or comprising a metal alcoholate is then introduced into the well through the tubing or casing, and is forced into the formation by pumping down another charge of oil, or by applying pressure to the well inany other known manner. The solution will diffuse into the formation water, forming by hydrolysis the desired water-insoluble metallic hydroxide, and an alcohol. When the flow of the well is reversed by pumping or swabbing, the water horizon will remain effectively plugged by said precipitate, while any part of the solution which may inadvertently have entered the oil horizon will be flushed out unchanged.

In sealing oil gas-bearing layers, the same procedure may be followed, if the gas-bearing formation is sufllciently' wet, as is often the case. If this formation, however, is dry or substantially dry, an aqueous liquid, such as water or brine, may be introduced into the well and forced into the formation before or after the injection of the treating metal alcoholate solution. The hydrolysis of the metal alcoholates in the pores of the formation then takes place as described above. In order to insure the formation of the insoluble metallic hydroxide as far back within the formation as possible, it may sometimes be desirable to introduce into the well and force into the formation a charge of a neutral material, such as oil, between the charges of the treating solution and of the aqueous liquid. It is understood that aqueous charges may be injected intothe formation also while treating water-bearing strata, for example, to control the rate of the hydrolysis reaction. I

Instead of pumping down the alcoholates or their solutions and/or the aqueous charge, these materials may be introduced. into the well in suitable containers and dumped at the desired levels.

In treating water and gas layers closely adjacent oil horizons, it may happen that a portion of the treating metal alcoholate solution is inadvertently forced into an oil'sand, and is hydrolyzed within said sand by the interaction with. the following aqueous charge, or with formation waters sometimes present in oil layers. Since, however, the metallic hydroxide, precipitated thereby, is soluble in acid, oil sands plugged in this manner can be easily restored to production by a subsequent acid treatment applied at the v desired level.

(1) By varying the concentration of the metal alcoholate in the solution which is forced into the formation, higher concentrations giving a higher rate of hydrolysis.

(2) By properly selecting the particular metal alcoholate used in each case. Alcoholates formed of higher alcohols, or of substituted or polyhydric alcohols have generally a slower rate of hydrolysis than those formed of lower monohydric alcohols. The rate of hydrolysis of any given alcoholate can also be controlled by using it in admixture with other alcoholates. Thus, for example, the hydrolysis rate of aluminum secondary amyl alcoholate may be considerably reduced by admixing thereto proper amounts of the aluminum alcoholate of ethylene glycol, which has a slow hydrolysis rate.

Although the process of this invention has been described with regard to its uses in well-drilling practice, it is obvious that it can equally well be applied for sealing off and decreasing the permeability of any desired ground formations. Thus, the present invention may have a practical application in building canals, sluices or dykes in porous soil, where it is desirable to stop the percolation of water through the sand, or in constructing landing piers, tunnels, etc., in ground formations which are not sufficiently impervious wherein M is any metal forming a water-insoluble hydroxide; O and C are an oxygen and 'a carbon atom, respectively; R1, R2, and R3 are radicals selected from the group consisting of hydrogen, alkyl, aryl, substituted alkyl, and substituted aryl radicals, -..'\d :r: and y are subscripts satisfying valence requirements, and forming within said formation a water-insoluble hydroxide by reaction of said alcoholate with water.

3. In a process for sealing off water and gasbearing formations traversed by a well, the steps of introducing into the "well a treating nonaqueous liquid comprising an alcoholate of a metal forming water-insoluble hydroxides, ap-- plying pressure to force said liquid into the formations, and introducing into the well and forcing into theformations an aqueous liquid, to intermingle said non-aqueous liquid and said aqueous liquid within the formations, whereby a water-insoluble metallic hydroxide is precipitated within said formations.

4. In a process for sealing of! water and gasbearing formations traversed by a well, the steps of introducing into the well and forcing in said formations alternate charges of a treating nonaqueous liquid comprising an alcohoiate of a metal forming water-insoluble hydroxides, of oil, and of an aqueous liquid, to 'eflect a delayed mingling of said treating liquid with said aqueous liquid to take place within the formation, and whereby a water-insoluble hydroxide is formed therein by reaction between said two liquids.

5. In a process for decreasing the permeability of a porous formation, the steps of introducing thereinto a mixture of alcoholates of metals forming water-insoluble hydroxides, said mixture comprising at least one relatively slowly-hydrolyzabie alcoholate of a higher alcohol, and slowly forming within said formation a water-insoluble hydroxide by reaction of said mixture with water.

6. In a process for decreasing the permeability of a porous formation, the steps of introducing thereinto a mixture of alcoholates of metals forming water-insoluble hydroxides, said mixture comprising at least one relatively slowly-hydrolyzable alcoholate of a substituted alcohol, and slowly forming within said formation a water-insoluble hydroxide by reaction of said mixture with water.

7. In a process for decreasing the permeability of a porous formation, the steps of introducing therelnto a mixture of aicoholates of metals forming water-insoluble hydroxides, said mixture comprising at least one relatively slowly-hydrolyzable alcoholate of a polyhydric alcohol, and slowly forming within said formation a waterinsoluble hydroxide by reaction of said mixture with water.

FRANKLIN A. BENT. ALBERT G. LOOMIS. HOWARD C. LAWTON.

DISCLAIMER 2,169,4586Franklin August 15, 1939. Disclaimer filed October 1, 1940, by the assignee,

Development Company. Hereby enters from the scope of claim 2 all processes A. Bent, Albert G. Loomis, alif. Mn'rnon or SEALING 0m WATER AND Gas Lxrnss.

this disclaimer to claim 1 of said Letters for decreasing the permeability of a porous and Howard C. Lawton, Berkeley Patent dated Shell Patent, and disclaims formation except those wherein there is introduced into the porous formation a metal alcoholate having the formula recited in claim 2, but wherein not more than one of the three radicals R R and R is h drogen,

g of! water an gas bearin those wherein there is introduced into the w processes for se and disclaims from the scope of claim 3 all formations traversed by a well excelpt a metal alcoholate having the form a consisting of hydrogen, alkyl,

wherein M is any metal forming a water-insoluble hydroxide; O and C are an oxygen and a carbon atom, respectively; R R and R are radicals selected from the aryl, substituted oup alkyl, and substituted aryl ra 'oals,

not more than one of which radicals is hydrogen, and a: and y are subscripts satisfying valence r uirements.

'ai Gazette October 29, 1940.1

aqueous liquid within the formations, whereby a water-insoluble metallic hydroxide is precipitated within said formations.

4. In a process for sealing of! water and gasbearing formations traversed by a well, the steps of introducing into the well and forcing in said formations alternate charges of a treating nonaqueous liquid comprising an alcohoiate of a metal forming water-insoluble hydroxides, of oil, and of an aqueous liquid, to 'eflect a delayed mingling of said treating liquid with said aqueous liquid to take place within the formation, and whereby a water-insoluble hydroxide is formed therein by reaction between said two liquids.

5. In a process for decreasing the permeability of a porous formation, the steps of introducing thereinto a mixture of alcoholates of metals forming water-insoluble hydroxides, said mixture comprising at least one relatively slowly-hydrolyzabie alcoholate of a higher alcohol, and slowly forming within said formation a water-insoluble hydroxide by reaction of said mixture with water.

6. In a process for decreasing the permeability of a porous formation, the steps of introducing thereinto a mixture of alcoholates of metals forming water-insoluble hydroxides, said mixture comprising at least one relatively slowly-hydrolyzable alcoholate of a substituted alcohol, and slowly forming within said formation a water-insoluble hydroxide by reaction of said mixture with water.

7. In a process for decreasing the permeability of a porous formation, the steps of introducing therelnto a mixture of aicoholates of metals forming water-insoluble hydroxides, said mixture comprising at least one relatively slowly-hydrolyzable alcoholate of a polyhydric alcohol, and slowly forming within said formation a waterinsoluble hydroxide by reaction of said mixture with water.

FRANKLIN A. BENT. ALBERT G. LOOMIS. HOWARD C. LAWTON.

DISCLAIMER 2,169,4586Franklin August 15, 1939. Disclaimer filed October 1, 1940, by the assignee,

Development Company. Hereby enters from the scope of claim 2 all processes A. Bent, Albert G. Loomis, alif. Mn'rnon or SEALING 0m WATER AND Gas Lxrnss.

this disclaimer to claim 1 of said Letters for decreasing the permeability of a porous and Howard C. Lawton, Berkeley Patent dated Shell Patent, and disclaims formation except those wherein there is introduced into the porous formation a metal alcoholate having the formula recited in claim 2, but wherein not more than one of the three radicals R R and R is h drogen,

g of! water an gas bearin those wherein there is introduced into the w processes for se and disclaims from the scope of claim 3 all formations traversed by a well excelpt a metal alcoholate having the form a consisting of hydrogen, alkyl,

wherein M is any metal forming a water-insoluble hydroxide; O and C are an oxygen and a carbon atom, respectively; R R and R are radicals selected from the aryl, substituted oup alkyl, and substituted aryl ra 'oals,

not more than one of which radicals is hydrogen, and a: and y are subscripts satisfying valence r uirements.

'ai Gazette October 29, 1940.1 

